Manufacture of alcohols from their corresponding alkylenes



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MANUFACTURE OF ALCOHOLS FROM THEIR CORRESPONDING ALKYLENES Joseph Stanley, Jackson Heights, N. Y., assignor to W. A. Clean Corporation, a corporation of New Jersey No Drawing. Application May 1, 1935,

Serial No. 19,174

25 Claims.

The present invention relates to the manufacture of alcohols from their corresponding alkylenes or oleflnes. Particularly one of the objects of this invention is the conversion of ethylthe boric acid which I reuse for the same p p se. After the reaction between the alkyl sulphate and boric acid has taken place, the reactor can be put under diminished pressure and thus cause.

5 8116111150 ethyl a cohol. the volatilization of the ethyl borate below its 5 Oleflnes or alkylenes have been converted into normal boiling point of 120 degrees centigrade. their corresponding alcohols by causing them to By distilling off the ethyl borate as soon as formed react with a mineral acid like sulphuric or phosunder diminished pressure I not only bring the phoric acid to form the corresponding esters, direaction to better completion, but I further miniluting said esters with water, and boiling ofl the mize any slight decomposition of the sulphuric 10 alcohol produced by the hydrolysis. The diluted acid by causing the ethyl borate to boil at a lower mineral acid left behind after distilling off the temperature. alcohol, was reconcentrated, and reused for the I do not limit myself to the preparation of absorption of more olefine. It is an object of this ethyl alcohol, but include the preparation of any invention to do away with these long and expenalkyl alcohol from its corresponding olefine. In sive processes of dilution, distillation, and reconthe preparation of the higher dialkyl sulphates, centratlon by making use of certain chemical reand trialkyl borates I find that low temperatures actions of whichlamthe discoverer. and high vacua are most essential, as otherwise I have discovered that an alkyl sulphate, an decomposition of the dialkyl sulphate may take alkyl phosphate, or an alkyl aryl sulphonate react place during its transformation into its corre- 20 with boric acid to form the corresponding alkyl spending borate. borates. For example the ethyl sulphates, the I find it to advantage sometimes to mix in with ethyl phosphates, and ethyl phenyl sulphonate the boric acid a proportion of metaboric acid,

when mixed with boric acid, and heated to 110 .pyroboric acid, or even boric oxide before I use to 140 degrees centigrade liberate ethyl borate, it for the dealkylation of the mineral acid esters 25 in accordance with the following chemical reacdescribed above. tions represented by the following chemical equa- I flnd it to advantage for certain purposes to tions: make the conversion of alkylene into its corresponding alcohol continuous. For example I can 3SOz(OC2H5)2+B3(OH) a= lead a proper and continuous stream of ethylene,

503(0021'15) (OH) +B OC3H5 3 and a proper and continuous stream of boric 3S02(OC2H5) (OH) +B(OI-I) 3SO2(OH) +B(OC H5) acid into a reactor containing sulphuric acid of ssoflocaH )2+2B(0H) 2 2 3 the proper concentration at the proper tempera- 5 35 (OH) 2B(OC H5) ture and pressure. This causes a volatilization ofapomc H5) 2B( 2 2+ 2 3 the ethyl borate with the excess ethylene which 35 2 3+ 0H)3 are driven out of the reactor into a condenser Pomc H 3PO(OC2H5) (OH) 2+2B(OC2H5) 3 which causes the condensation of the ethyl borate, 5 3+B(OH)3=PO(OH)3+B(OCZH5)3 the ethylene is not condensed however but it is 40 H) (OCzHs) 2+2B(3O1fg (cg-H 2 recycled into the reactor. The condensed ethyl- 40 3PO(OH )3+ Bwczm) 3 borate is sent to the hydrolyzer where it is mixed )2(OC2H5) +B(OH)3= with the stoichiometric proportion .of water and 3+B(C2H5) 3 hydrolyzed into boric acid and ethyl alcohol. The (002m) +B(OH) 3: alcohol is distilled off and the residue of boric acid 3802((36115) (0H)+B(OCH5)3 recycled intothe reactor. The same sulphuric 45 After the removal of the ethyl b r t by and boric acids can thus be used to transform an tillation, the acid or acid ester remaining behind almost efinite amount of ethylene into et y sufiers no dilution, and can be used without any alcohol treatment for the absorption of more ethylene. A novelty of this invention-1s that I can dealso The distilled ethyl borate is then mixed with the v at a kyl sulp tes a d ph sp at s by m s stoichiometric proportion of water to hydrolyze 'Of boric ac d using el e y low temperatures,

it into boric acid and ethyl alcohol, and the boric and thus conserve the sulphuric acid or phosacid separated from the alcohol by filtration, phoric acid from decomposition and/or volatilifreezing, or distillation, or a combination of these zation. Another novelty of this invention is that processes. I thus recover substantially all of I can dealkylate alkyl sulphates or phosphates 55 without the necessity of diluting these esters with water. Another novelty of this invention is that I do not have to reconcentrate any dilute sulphuric or phosphoric acid, because said acids are never diluted with water to start with. Another novelty of this invention is'that the alkyl borate is readily hydrolyzed with the stoichiometric proportion of water to produce a solutionof boric acid in substantially anhydrous alcohol which can be readily separated from the boric acid in substantially anhydrous form, thus doing away with the necessity of expensive rectification of the dilute alcohol solutions which are obtained by other processes, not to mention doing away with the necessity of chemical or azeotropic dehydration of the rectified alcohol to make it substantially anhydrous. A further novelty of this invention is that I convert a dim-- cultly hydrolyzable and volatile ester like ethyl sulphate into one which is more easily hydrolyzable and volatile like ethyl borate.

To illustrate the practice of the invention I shall give an example. Ethylene was passed into heated sulphuric acid in the well known way until the proper conversion into ethyl sulphates had taken place. -A vacuum was then applied to the above liquid permitting the distillation and subsequent condensation of the diethyl sulphate. Two hundred grams of this diethyl sulphate were collected and added to 27 grams of boric acid. The mixture was heated at 120 to 130 degrees centigrade for a short time and then a slight vacuum was applied whereby the ethyl borate distilled oif and was condensed, 61 grams of ethyl borate being collected. This ethyl borate was then mixed with 23 grams of water which produced 84 grams of a solution of boric acid in absolute alcohol. The absolute alcohol was distilled off and it measured 70 cubic centimeters. The boric acid residue weighed 24.5 grams. The above alcohol was next made alkaline with potassium hydroxide to fix any boric acid that may have distilled over with it, and redistilled.

I claim:

1. A process for producing alkyl borates comprising reacting an alkyl ester of an acid of the group consisting of sulphuric, phosphoric, and aryl sulphonic with boric acid, and separating the alkyl borate by distillation.

2. A process for producing alkyl borates comprising reacting an alkyl ester of sulphuric acid with boric acid, and separating the alkyl borate by distillation.

3. A process for producing alkyl borates comprising reacting an alkyl ester of phosphoric acid with boric acid, and separating the alkyl borate by distillation.

4. A process for producing alkyl borates comprising reacting an alkyl ester of an aryl sulphonic acid with boric acid, and separating the alkyl borate by distillation.

5. A process for producing ethyl alcohol comprising the conversion of ethylene to an ethyl ester of a strong non-oxidizing inorganic acid, deethylating said ester by means of boric acid thereby producing ethyl borate, distilling. ofi the ethyl borate, and hydrolyzing said ethyl borate producing ethyl alcohol and regenerating the boric acid.

6. A process which comprises dealkylating an alkyl sulphate with boric acid producing an alkyl borate removing said alkyl borate by distillation, and reusing the dealkylated reaction mixture by reallqlating with more alkylene.

7. A process which comprises dealkylating an alkyl phosphate with boric acid producing an alkyl borate removing said alkyl borate by distillation, and reusing the dealkylated reaction mixture by realkylating with more alkylene.

8. A process which comprises dealkylating an alkyl aryl sulphonate with boric acid producing an alkyl borate removing said alkyl borate by distillation, and reusing the dealkylated reaction mixture by realkylating with more alkylene.

9. A.continuous process for producing ethyl alcohol from ethylene comprising the passing of a continuous stream of ethylene and boric acid into sulphuric acid and volatilizing the ethyl borate formed with the excess ethylene, condensing theborate ester, but recycling the excess ethylene into the acid, the condensed borate ester being continuously reacted with the stoichiometric proportion of water thereby reforming the boric acid, and continuously distilling off the ethyl alcohol produced, while at the same time continuously returning the reformed boric acid to the ethylene absorption reactor.

10. A continuous process for producing ethyl alcohol from ethylene comprising the passing of a continuous stream of ethylene and boric acid into hot sulphuric acid and volatilizing the ethyl borate formed with the excess ethylene, condensing the borate ester, but recycling the excess ethylene into the acid, the condensed borate ester being continuously reacted with the stoichiometric proportion of water thereby reforming the boric acid, and continuously distilling ofi the ethyl alcohol produced, while at the same time continuously returning the reformed boric acid.

to the ethylene absorption reactor.

11. A continuous process for producing ethyl alcohol from ethylene comprising the passing of a continuous stream of ethylene and boric acid into substantially sulphuric acid and volatilizing the ethyl borate formed with the excess ethylene, condensing the borate ester, but recycling the excess ethylene into the acid, the condensed borate ester being continuously reacted with the stoichiometric proportion of water thereby reforming the boric acid, and continuously distilling 01f the ethyl alcohol produced, while at the same time continuously returning the reformed boric acid to the ethylene absorption reactor.

12. A continuous process for producing ethyl alcohol from ethylene comprising the passing of a. continuous stream of ethylene and boric acid into phosphoric acid and volatilizing the ethyl borate formed with the excess ethylene, condensing the borate ester, but recycling the excess ethylene into the acid, the condensed borate ester being continuously reacted with the stoichiometric proportion of water thereby reforming the boric acid, and continuously distilling oil. the ethyl alcohol produced, while at the same time continuously returning the reformed boric acid to the ethylene absorption reactor.

13. A continuous process for producing ethyl alcohol from ethylene comprising the passing of a continuous stream of ethylene and boric acid into hot phosphoric acid and volatilizing the ethyl borate formed with the excess ethylene, condensing the borate ester, but recycling the excess ethylene into the acid, the condensed borate ester being continuously reacted with the stoichiometric proportion of water thereby reforming the boric acid, and continuously returning the reformed boric acid to the ethylene absorption reactor.

14. A continuous process for producing ethyl alcohol from ethylene comprising the passing of a continuous stream of ethylene and boric acid into-substantially 100% phosphoric acid and volatilizing the ethyl borate formed with the excess ethylene, condensing the borate ester, but recycling the excess ethylene into the acid, the condensed borate ester being continuously reacted with the stoichiometric proportion of water thereby reforming the boric acid, and continuously distilling oil the ethyl alcohol produced, while at the sametime continuously returning the reformed boric acid to the ethylene absorption reactor.

15. A continuous process for producing ethyl alcohol from ethylene comprising the passing of a continuous stream of ethylene and boric acid into an aryl sulphonic acid and volatilizing the ethyl borate formed with the excess ethylene, condensing the borate ester, but recycling the excess ethylene into the acid, the condensed borate ester being continuously reacted with the stoichiometric proportion of water thereby reforming the boric acid, and continuously distilling ofi the ethyl alcohol produced, while at the same time continuously returning the reformed boric acid to the ethylene absorption reactor.

16. A continuous process for producing ethyl alcohol from ethylene comprising the passing of a continuous stream of ethylene and boric acid into a hot aryl sulphonic acid and volatilizing the ethyl borate formed with the excess ethylene,

condensing the borate ester, but recycling the excess ethylene into the acid, the condensed borate ester being continuously reacted with the stoichiometric proportion of water thereby reforming the boric acid, and continuously distilling off the ethyl alcohol produced, while at the same time continuously returning the reformed boric acid to the ethylene absorption reactor.

1'7. A continuous process for producing ethyl alcohol from ethylene comprising the passing of a continuous stream of ethylene and boric acid into a substantially anhydrous aryl sulphonic acid and volatilizing the ethyl borate formed with the excess ethylene condensing the borate ester, but recycling the excess ethylene into the acid, the condensed borate ester being continuously reacted with the stoichiometric proportion of water thereby reforming the boric acid,

and continuously distilling oil the ethyl alcohol produced, while at the same time continuously 19. A process for converting compounds with an oleflnic bond to the corresponding alcohols comprising reacting said oleflnes with sulphuric acid thereby forming an ester of sulphuric acid, and then allowing said sulphate ester to react with boric acid thereby forming the corresponding borate ester, and regenerating the sulphuric acid, said borate ester being then reacted with water to form boric acid and the corresponding alcohol.

20. A process for converting compounds with an olefinio bond to the corresponding alcohols comprising reacting said olefines with phosphoric acid thereby forming an ester of phosphoric acid. and then allowing said phosphate ester to react with boric acid thereby forming the corresponding borate ester, and regenerating the phosphoric acid, said borate ester being then reacted with water to form boric acid and the corresponding alcohol.

21. A process for converting compounds with an olefinic bond to the corresponding alcohols comprising reacting said oleflnes with an aryl sulphonic acid thereby forming an ester of the corresponding aryl sulphonic acid, and then a1- lowing said sulphonate ester to react with boric acid thereby forming the corresponding borate ester, and regenerating the sulphonic acid, said borate ester being then reacted with water to form boric acid and the corresponding alcohol.

22. A process for producing substantially anhydrous ethyl alcohol comprising the conversion of ethylene to an ethyl ester of an acid of the group consisting of sulphuric, phosphoric, and aryl sulphonic, dealkylating said ester by means of boric acid, thereby producing ethyl borate, distilling off the ethyl borate, and hydrolyzing said ethyl borate producing substantially anhydrous ethyl alcohol and regenerating the boric acid.

23. A process for producing substantially anhydrous ethyl alcohol comprising the conversion producing substantially anhydrous ethyl alcohol and regenerating the boricacid.

25. A process for producing substantially an hydrous ethyl alcohol comprising the conversion of ethylene to an ethyl ester of an aryl sulphonic acid, dealkylating said ester by means of boric acid, thereby producing ethyl borate, distilling oil the ethyl borate, and hydrolyzing said ethyl borate producing substantially anhydrous ethyl alcohol and regenerating the boric acid.

JOSEPH STANLEY. 

